Coupled diusion and mechanics in battery electrodes

Thesis (Ph.D.)--University of Washington, 2016-08

Ad-atoms and their enhancement effects on Pt activity for formic acid oxidation

Formic acid oxidation has been widely studied at Pt as a model reaction to understand fundamental aspects of electrocatalytic reactions in fuel cells. Electrocatalytic oxidation of formic acid takes place through two parallel pathways (direct and indirect). The indirect pathway proceeds via CO as an intermediate, which is known to be responsible for the poisoning of Pt and its consequent decrease in activity. Surface modification of Pt with ad-atoms is known to hinder this poisoning and promote the direct pathway. The incorporation of polymers (polyaniline, polycarbazole, polyindole) as supports also increases activity. Irreversibly adsorbed Sb and Bi on Pt are known to show high electrocatalytic activity for formic acid oxidation. This work presents the dependence of Sb and Bi irreversible adsorption on immersion time, metal solution concentration and pH. The activity of Sb and Bi modified Pt was correlated against immersion time and percent coverage of Pt by ad-atoms. Polyaniline support effects in combination with a Bi modified Pt catalyst showed enhancement in oxidation current compared to Pt-Bi.

MOLECULAR MASS MANIPULATION ENABLED BY GRAPHENE BASED NANOSTRUCTURES

The surge of interest in graphene, as epitomized by the Nobel Prize in Physics in 2010, is attributed to its extraordinary properties. Graphene is ultrathin, mechanically tough, and has amendable surface chemistry. These features make graphene and graphene based nanostructure an ideal candidate for the use of molecular mass manipulation. The controllable and programmable molecular mass manipulation is crucial in enabling future graphene based applications, however is challenging to achieve. This dissertation studies several aspects in molecular mass manipulation including mass transportation, patterning and storage. For molecular mass transportation, two methods based on carbon nanoscroll are demonstrated to be effective. They are torsional buckling instability assisted transportation and surface energy induced radial shrinkage. To achieve a more controllable transportation, a fundamental law of direction transport of molecular mass by straining basal graphene is studied. For molecular mass patterning, we reveal a barrier effect of line defects in graphene, which can enable molecular confining and patterning in a domain of desirable geometry. Such a strategy makes controllable patterning feasible for various types of molecules. For molecular mass storage, we propose a novel partially hydrogenated bilayer graphene structure which has large capacity for mass uptake. Also the mass release can be achieved by simply stretching the structure. Therefore the mass uptake and release is reversible. This kind of structure is crucial in enabling hydrogen fuel based technology. Lastly, spontaneous nanofluidic channel formation enabled by patterned hydrogenation is studied. This novel strategy enables programmable channel formation with pre-defined complex geometry.